TWI565817B - A film forming apparatus, a sputtering cathode, and a thin film forming method - Google Patents

Description

Thin film forming device, sputtering cathode and film forming method

The present invention relates to a thin film forming apparatus, a sputtering cathode, and a thin film forming method, and more particularly to a thin film forming apparatus, a sputtering cathode, and a thin film forming method capable of forming an optical multilayer film on a substrate at a high deposition rate.

A method of forming a metal compound thin film by sputtering, and RF reactive sputtering using a high-frequency power source to introduce a reactive gas to a metal compound target or a metal target and forming a thin film by reactive sputtering or using a direct current is known. A DC reactive sputtering method in which a power source introduces a reactive gas into a metal compound target or a metal target and forms a thin film by reactive sputtering.

Here, FIG. 8 shows the relationship between the reactive gas flow rate/total gas flow rate ratio and the film formation rate (film formation rate). Here, the reactive gas flow rate and the total gas flow rate refer to the gas flow rate in the vicinity of the target. In Fig. 8, the region where the ratio of the reactive gas flow rate is low is the region of the metal mode A which is substantially the same film formation rate as when the flow rate of the reactive gas is zero. In the region of the metal mode, the film formation rate is slow to the change in the value of the reactive gas flow rate.

In a region where the ratio of the reactive gas flow rate is higher than the metal mode, the transition region pattern B is rapidly decreased by increasing the ratio of the flow rate of the reactive gas, and if the ratio of the reactive gas flow rate is further increased, the ratio is increased. The film rate is a low value and stable region, and the change in the value of the reactive gas flow rate is a region of the retardation reactive mode C.

The above RF reactive sputtering method or DC reactive sputtering method is performed by sputtering in the region of the reactive mode C of the graph of Fig. 8, and is compared with the case where a metal thin film is formed without introducing a reactive gas. Film formation rate of /5~1/10.

As a technique for forming a high-quality optical multilayer film which reduces the film formation rate in such an RF reactive sputtering method or a DC reactive sputtering method, a sputtering method is known which is incorporated in a vacuum container. A radical source is provided, and a metal compound is formed by oxidizing a deposit on a sputtering target or a substrate from a metal target by a radical (see, for example, Patent Document 1).

The sputtering method described in Patent Document 1 separates a film formation region and a reaction region in a vacuum vessel in a space and pressure, and performs a sputtering reaction from a metal target in a film formation region to cause a reactive gas in the reaction region. The active species contacts the formed metal film to form a thin film of the metal compound.

According to the sputtering method described in Patent Document 1, since the reactive mode C of FIG. 8 is used in the metal mode A, the optical multilayer film can be formed at a high deposition rate.

However, according to the sputtering method of Patent Document 1, since the sputtering film formation region and the reaction region by oxidation and nitridation of radicals must be spatially separated and the substrate must be rotated at a high speed, the form of the device is limited to rotation. Rotary cylinder type of rack type. Therefore, it cannot be applied to a substrate facing type or an in-line type device. Therefore, the size of the substrate that can be mounted is limited to a small size, and it is difficult to form a large-sized substrate.

[Advanced technical literature]

Patent Document 1: Japanese Patent Laid-Open No. 2001-234338 (paragraph 0067 to 0072, Fig. 1)

The present invention has been made in view of the above circumstances, and an object thereof is to provide a thin film forming apparatus, a sputtering cathode, and a thin film forming method capable of forming an optical multilayer film on a large-sized substrate at a high film formation rate.

The inventors of the present invention have found an unexpected fact that the energy source for exciting a reactive gas into a plasma state has become a predetermined configuration as a result of intensive research on the arrangement of a target and an active seed source in a vacuum chamber. Even if the target and the active seed source are not separated from each other in space and pressure, and they are mutually influenced by electromagnetic force and pressure, they can be formed by sputtering in a metal mode or a migration mode mode in a reactive mode. A thin film of a metal compound, thereby completing the present invention.

That is, according to the invention of claim 1 of the patent application, a film forming apparatus is attached a film for forming a metal compound by sputtering on a substrate in a vacuum chamber, comprising: a target material in the vacuum chamber; a metal or a conductive metal compound; and an active species source; The targets interact with each other electromagnetically and under pressure to form an active species of a reactive gas; the active seed source includes a gas source for supplying the reactive gas, and supplies energy to the vacuum chamber to convert the reactivity The gas is excited into an energy source in a plasma state; the target is disposed opposite to the substrate between the substrate and the substrate at a distance of 40 mm or less and 400 mm or less; the energy source is between the vacuum chamber and the vacuum chamber Providing a dielectric window for supplying the energy into the vacuum chamber; the dielectric window is disposed parallel to the substrate or inclined to the target side at an angle of 90° or less with respect to the substrate Solve the above problems.

Conventional reactive sputtering in which a target material such as a metal is sputtered while introducing a reactive gas, and when the amount of introduction of the reactive gas is increased, a metal compound is formed on the surface of the target to cause a reaction at a low deposition rate. In view of the film formation method, the film formation method of the present invention can form a film of a metal compound by sputtering in a metal mode or a migration mode mode in a reactive mode, thereby enabling a high film formation rate. An optical multilayer film is formed.

That is, since there is an active seed source that is designed to interact with each other electromagnetically and under pressure, the plasma generated by applying a voltage to the target and the plasma generated by the active seed source The interaction, the plasma density in the region between the target and the substrate becomes higher. As a result, the amount of the active species of the sputtering gas such as Ar ⁺ around the target increases, and the sputtering efficiency is improved.

Further, since the sputtering efficiency is improved, a metal or a conductive metal compound is ejected from the surface of the target before the metal compound is formed on the surface of the target. Therefore, the formation of the metal compound on the surface of the target is suppressed, and the decrease in the film formation rate is prevented.

Further, since the active species of the reactive gas are generated from the active seed source, a high reaction rate can be obtained even with a small amount of reactive gas. As a result, even if the introduction amount of the reactive gas is reduced, the particles of the incomplete compound ejected from the target and the film formation of the incomplete compound formed by depositing the particles on the substrate can be sufficiently reacted. Yes, can be in metal mode or migration The region mode produces a metal compound film.

Moreover, the energy source is provided with a dielectric window for supplying energy into the vacuum chamber, and the dielectric window is arranged to be parallel to the substrate or to the target at an angle of less than 90° with respect to the substrate. Side tilt. Therefore, it is possible to simultaneously perform sputtering of a metal or a conductive metal compound target to cause particles of the incomplete compound ejected from the target to scatter in the direction of the substrate, and the particles of the incomplete compound are deposited on the substrate to form incomplete Conversion of the metal to the complete compound of the film former of the compound. As a result, it is not necessary to separate the target material from the active seed source in space and pressure, and it is possible to influence each other in electromagnetic force and pressure.

In this case, the dielectric window may be disposed to be inclined toward the target side at an angle of 30° or more with respect to the substrate, and the substrate may be positioned opposite to the energy source in a direction perpendicular to a direction in which the substrate is transported. Towards the location.

In this case, the substrate transfer unit that transports the substrate in the vacuum chamber may be provided, and at least one of the upstream side and the downstream side of the substrate in the transport direction of the substrate may be provided with the active seed source.

In this way, since at least one of the upstream side and the downstream side of the target material has an active seed source, the metal target can be simultaneously sputtered, and the particles of the incomplete compound ejected from the target can be scattered in the direction of the substrate. The conversion of the metal to the complete compound of the film formation of the incomplete compound formed by the particles of the complete compound deposited on the substrate can be set to be electromagnetic in each other without separating the target and the active seed source in space and pressure. And stress affect each other.

In this case, the substrate transfer unit that transports the substrate in the vacuum chamber may be provided, and the active seed source may be provided on the upstream side and the downstream side of the substrate in the transport direction of the substrate.

Further, a sputtering gas controller that controls a flow rate of the sputtering gas introduced into the target material and a reactive gas controller that controls a flow rate of the reactive gas may be provided independently of each other; and optically detected a film rate detecting portion; and a control device for receiving a signal from the detecting portion, at least independently controlling the sputtering power source and the sputtering gas The controller, the power source of the aforementioned active seed source, and the aforementioned reactive gas controller are used to control the film formation rate.

In this case, the energy source may also be a plasma source that generates plasma by inductive coupling or surface wave through the dielectric window.

According to the above configuration, the positional relationship between the radical source and the substrate and the target can be appropriately selected, and the thin film forming apparatus capable of forming the film under optimum conditions can be easily formed.

In this case, the active seed source may also be an inductively coupled plasma (ICP) radical source.

With the above configuration, it is possible to achieve a high film formation rate by a large-diameter plasma having a low pressure and a high density.

In this case, the thin film forming apparatus may be configured by an in-line sputtering apparatus including a plurality of film forming stations including the target and the upstream and downstream of the transfer direction of the substrate provided in the target. The aforementioned active species source of at least one of the sides.

Since it is constituted as described above, it is not necessary to form a device which forms a metal compound film at a high film formation rate while sputtering in a metal mode or a migration mode mode, and is configured as a conventional rotating frame type. As a result, the shape and size of the substrate are not limited, and a metal compound film can be formed on the large substrate at a high deposition rate.

In this case, the film formation station may further include a detection unit that optically detects the film formation rate, or may include a signal for receiving the detection unit from the film formation rate to control the individual film formation rates of the film formation stations. Control device.

According to the above configuration, the film formation rate feedback control can be performed by independently controlling the power source and gas flow rate of the sputtering and the power source and gas flow rate of the active seed source.

In this case, a sputtering unit may be provided in which the target material is sputtered in the vacuum chamber, and the particles of the incomplete compound are scattered from the target to the substrate by the sputtering; and the conversion unit is formed by In the vacuum chamber, an active species of a reactive gas generated by the active seed source is contacted with the particles to be converted into a complete compound of a metal; and the substrate can be formed on the substrate A film composed of a complete compound of the foregoing metal.

According to the above configuration, the target material and the active species source can be mutually influenced by electromagnetic force and pressure, and it is not necessary to separate the target material from the active seed source in space and pressure, so that a film of a simple composition can be formed. Device.

According to the invention of claim 11, a sputtering cathode is a thin film formed by sputtering on a substrate to form a metal compound, characterized by comprising: a target material composed of a metal or a conductive metal compound; And an active species source, which is formed by interacting with the target electromagnetically and under pressure to generate an active species of a reactive gas; the active seed source having a gas source for supplying the reactive gas and supplying energy to the foregoing An energy source for exciting the reactive gas into a plasma state in the vacuum chamber; wherein the target material is disposed opposite to the substrate at an interval of 40 mm or longer and 400 mm or less between the substrate and the substrate; Providing a dielectric window for supplying the energy to the outside of the energy source; the dielectric window is disposed parallel to the substrate or inclined to the target side at an angle of less than 90° with respect to the substrate This solves the aforementioned problems.

Conventional reactive sputtering in which a target material such as a metal is sputtered while introducing a reactive gas, and when the amount of introduction of the reactive gas is increased, a metal compound is formed on the surface of the target to cause a reaction at a low deposition rate. In view of the film formation method, the film formation method of the present invention can form a film of a metal compound by sputtering in a metal mode or a migration mode mode in a reactive mode, thereby enabling a high film formation rate. An optical multilayer film is formed.

That is, since there is an active seed source that is designed to interact with each other electromagnetically and under pressure, the plasma generated by applying a voltage to the target and the plasma generated by the active seed source The interaction, the plasma density in the region between the target and the substrate becomes higher. As a result, the amount of the active species of the sputtering gas such as Ar ⁺ around the target increases, and the sputtering efficiency is improved.

Further, since the sputtering efficiency is improved, a metal or a conductive metal compound is ejected from the surface of the target before the metal compound is formed on the surface of the target. Therefore, inhibiting metal compounds on the target table The formation of the surface prevents the film formation rate from decreasing.

Further, since the active species of the reactive gas are generated from the active seed source, a high reaction rate can be obtained even with a small amount of reactive gas. As a result, even if the introduction amount of the reactive gas is reduced, the particles of the incomplete compound which are ejected and the film formation of the incomplete compound in which the particles are deposited on the substrate can be sufficiently reacted, so that the metal mode or the migration region can be used. The pattern produces a metal compound film.

In this case, the target material and the active species may be disposed in the same space of the vacuum chamber, and the sputtered surface of the target which is sputtered may be located opposite to the active seed source to the substrate and the active seed source. At least one of an upstream side and a downstream side of the transfer direction of the substrate of the target.

According to the above configuration, the plasma density generated in the region between the target and the substrate can be increased by the interaction between the plasma generated by applying a voltage to the target and the plasma generated by the active seed source. The amount of Ar ⁺ around the target increases, which increases the sputtering efficiency.

According to a thirteenth aspect of the invention, there is provided a film forming method comprising: a sputtering step of sputtering a space between the substrate and the substrate at a distance of 40 mm or more and 400 mm or less in the vacuum chamber; a target made of a metal or a conductive metal compound, wherein the particles of the incomplete compound are scattered from the target to the substrate by the sputtering; and a composition conversion step is provided for use in the vacuum chamber Parallel to the substrate or inclined toward the target side at an angle of 90° with respect to the substrate to supply energy to the dielectric window in the vacuum chamber, so as to be electromagnetically arranged with the target An active species of a reactive gas generated by an active species of an active species that reacts with each other and reacts with each other in contact with each other to contact the particles to convert to a complete compound of a metal, comprising the above two steps on the substrate The above problem can be solved by forming a film composed of a complete compound of the above metal.

Conventional reactive sputtering in which a target material such as a metal is sputtered while introducing a reactive gas, and when the amount of introduction of the reactive gas is increased, a metal compound is formed on the surface of the target. In the reactive mode in which the film formation rate is low, film formation is achieved. In contrast, the film formation method of the present invention can form a metal compound by sputtering in a metal mode or a migration mode mode without using a reactive mode. The optical multilayer film can be formed at a high film formation rate.

That is, since there is an active seed source that is designed to interact with each other electromagnetically and under pressure, the plasma generated by applying a voltage to the target and the plasma generated by the active seed source The interaction, the plasma density in the region between the target and the substrate becomes higher. As a result, the amount of the active species of the sputtering gas such as Ar ⁺ around the target increases, and the sputtering efficiency is improved.

Further, since the sputtering efficiency is improved, a metal or a conductive metal compound is ejected from the surface of the target before the metal compound is formed on the surface of the target. Therefore, the formation of the metal compound on the surface of the target is suppressed, and the decrease in the film formation rate is prevented.

Further, since the active species of the reactive gas are generated from the active seed source, a high reaction rate can be obtained even with a small amount of reactive gas. As a result, even if the introduction amount of the reactive gas is reduced, the particles of the incomplete compound which are ejected and the film formation of the incomplete compound in which the particles are deposited on the substrate can be sufficiently reacted. Therefore, the metal compound film can be formed in a metal mode or a migration region mode.

Further, by using an active species of a reactive gas generated by an active seed source which is electromagnetically and pressure-affected with each other, the thin film formation of the incomplete compound which is deposited on the substrate by the particles is borrowed. This conversion is a complete compound of metal, so that the target and the active species source can be mutually influenced by electromagnetic and pressure, and the active seed source and the target need not be spatially and pressure-separated, so that a simple composition can be used. The film forming device is used to form a film.

At this time, the reverse film formation step may be performed after the composition conversion step, wherein the sputtering step and the composition conversion step are repeated in parallel several times.

According to the above configuration, the metal compound can be formed into a film without sputtering in a metal mode or a migration region mode in a reactive mode, and a metal compound film having a desired film thickness can be obtained.

In this case, it is also possible to perform an in-line thin film having a plurality of film forming stations before the sputtering step. a step of introducing the substrate into the substrate, wherein the film formation station includes the active seed source of at least one of the target and the upstream side and the downstream side of the substrate in the transport direction of the target; and performing the in-situ film formation step The film forming step in the station performs the sputtering step, the composition conversion step, and the reverse film forming step while the substrate is transported at a constant speed in the film forming station, and transports the substrate to the substrate. a transfer step of the film formation station on the downstream side; a film formation step of repeating the in-station film formation step and the transfer step; and performing the above-described station formation at the film formation station located at the most downstream of the substrate transfer direction After the film step, a step of discharging the substrate to the atmosphere is performed.

According to the above configuration, the metal compound multilayer film having a desired number of layers can be formed by appropriately selecting the number of film formation stations.

Conventional reactive sputtering in which a target material such as a metal is sputtered while introducing a reactive gas, and when the amount of introduction of the reactive gas is increased, a metal compound is formed on the surface of the target to cause a reaction at a low deposition rate. In view of the film formation method, the film formation method of the present invention can form a film of a metal compound by sputtering in a metal mode or a migration mode mode in a reactive mode, thereby enabling a high film formation rate. An optical multilayer film is formed.

That is, since there is an active seed source that is designed to interact with each other electromagnetically and under pressure, the plasma generated by applying a voltage to the target and the plasma generated by the active seed source The interaction, the plasma density in the region between the target and the substrate becomes higher. As a result, the amount of the active species of the sputtering gas such as Ar ⁺ around the target increases, and the sputtering efficiency is improved.

Further, since the sputtering efficiency is improved, a metal or a conductive metal compound is ejected from the surface of the target before the metal compound is formed on the surface of the target. Therefore, the formation of the metal compound on the surface of the target is suppressed, and the decrease in the film formation rate is prevented.

Further, since the active species of the reactive gas are generated from the active seed source, a high reaction rate can be obtained even with a small amount of reactive gas. As a result, even if the introduction amount of the reactive gas is reduced, the particles of the incomplete compound which are ejected from the target can be formed by depositing the particles on the substrate. The film formation of the incomplete compound is sufficiently reacted. Therefore, the metal compound film can be formed in a metal mode or a migration region mode.

A‧‧‧ filming effective area

D‧‧‧Distance

ST, ST1~n‧‧‧ filming station

1,1'‧‧‧ Sputtering device

11‧‧‧Load lock chamber

12,13,32,33‧‧‧ gate valve

14,34‧‧‧Rotary pump

21‧‧‧ Filming room

22‧‧‧Loading Space Department

23‧‧‧Unloading Space Department

31‧‧‧ Unloading room

43‧‧‧Substrate

61‧‧‧ Target Agency

62a, 62b‧‧‧Magnetron Sputtering Electrodes

63a, 63b‧‧‧ targets

64‧‧‧AC power supply

65,76‧‧‧ gas bottles

66,77‧‧‧Flow Controller

75, 95a, 95b‧‧‧ piping

80‧‧‧Free radical source

80A‧‧‧Antenna housing room

81‧‧‧Box

83‧‧‧Dielectric board

84‧‧‧Fixed frame

85a, 85b‧‧‧Antenna

86a, 86b‧‧‧ lead section

87‧‧‧match box

87a, 87b‧‧‧variable capacitor

88‧‧‧ Fixtures

88a, 88b‧‧‧ fixed plate

88c, 88d‧‧‧ fixing bolts

89‧‧‧High frequency power supply

95‧‧‧vacuum pump

Fig. 1 is an explanatory view showing an in-line sputtering apparatus according to an embodiment of the present invention.

Fig. 2 is an enlarged explanatory view showing the configuration of a film formation station of the in-line sputtering apparatus according to the embodiment of the present invention.

Fig. 3 is a schematic explanatory view showing the configuration of a radical source according to an embodiment of the present invention.

Fig. 4 is a schematic explanatory view showing the configuration of a radical source according to an embodiment of the present invention.

Fig. 5 is an explanatory view showing an in-line type sputtering apparatus according to another embodiment of the present invention.

6 is a graph showing the reflectance of the multilayer AR film formed in Example 9 at each wavelength, and the Si ₃ N ₄ having a first layer of a physical film thickness of 123.9 nm and the second layer being a physical film thickness of 164.3 nm. _{2. A} graph in which the third layer is a Si ₅ N ₄ film having a physical film thickness of 99.5 nm, and a film of a multilayer AR film having a fourth layer of SiO ₂ having a physical film thickness of 73.2 nm is designed to reflect the reflectance at each wavelength.

Fig. 7 is a graph showing the relationship between the oxygen partial pressure and the target voltage in the case where the oxygen flow rate is increased by using the in-line sputtering apparatus according to an embodiment of the present invention.

Fig. 8 is a graph showing the relationship between the reactive gas flow rate/total gas flow ratio in general sputtering and the film formation rate (film formation rate).

Hereinafter, embodiments of the present invention will be described with reference to the drawings. Further, the members, the configurations, and the like described below are not limited to the present invention, and various changes can be made in accordance with the gist of the present invention.

In the present specification, the reactive species of a reactive gas refers to a highly reactive particle generated by a high-speed electron collision of a reactive gas molecule or an atom in a plasma to cause a reaction such as ionization, dissociation, adhesion, and excitation, and includes a reaction. Ionic ions, free radicals, excited species, etc.

The radical of the reactive gas means a radical which is more active than the reactive gas molecule, and includes a radical of a molecular ion, an atom, and an inner shell electron of the reactive gas in an excited state.

(film forming device)

The sputtering apparatus 1 as the film forming apparatus of the present embodiment is a load lock type in-line type sputtering apparatus, and includes a load lock chamber 11, a film formation chamber 21, an unloading chamber 31, and A substrate transfer device (not shown) is configured.

The load lock chamber 11 is provided with a gate valve 12 for opening the lock lock chamber 11 to the atmosphere, a gate valve 13 provided between the film forming chamber 21, and a rotary pump 14 for exhausting the load lock chamber 11.

The unloading chamber 31 includes a gate valve 32 for opening the unloading chamber 31 to the atmosphere, a gate valve 33 provided between the film forming chamber 21, and a rotary pump 34 for exhausting the unloading chamber 31.

The substrate transfer device (not shown) is configured by a known substrate transfer device for an in-line type sputtering device, and includes a substrate holder (not shown) that holds the substrate 43 and a substrate transfer mechanism (not shown). By the substrate transfer device, the substrate 43 is introduced into the load lock chamber 11, the film formation chamber 21, and the unload chamber 31 from the atmosphere, and then transported to the atmosphere.

The fixed substrate 43 is held by a substrate holder (not shown).

The substrate 43 is composed of a large-sized optical member, a large-sized architectural window glass, and a large-sized FPD (flat panel display).

In the substrate holder (not shown), a single substrate 43 may be fixed, or a plurality of sheets, for example, four substrates having a size of four divided into two in a vertical and horizontal direction, may be fixed.

The film forming chamber 21 is connected to a plurality of film forming stations ST (ST1 to STn) (n is a positive integer), and both ends of the film forming chamber 21 are connected to the load lock chamber 11 and the unloading chamber 31 through the gate valves 13 and 33. A piping 95b for exhaust gas is connected to the bottom surface of the film forming chamber 21, and a vacuum pump 95 for exhausting the inside of the film forming chamber 21 is connected to the piping 95b. The degree of vacuum in the film forming chamber 21 can be adjusted by the vacuum pump 95 and a controller (not shown).

The film forming chamber 21 is constituted by a hollow casing extending in the conveying direction of the substrate 43, and a plurality of connecting space portions 22 at the end portions of the loading lock chamber 11 and the unloading space portion 23 at the end portions of the unloading chamber 31 are connected to each other. Film forming stations ST (ST1~STn).

The film formation station ST is composed of a hollow casing that is formed to be open to the film formation station ST or the loading space portion 22 and the unloading space portion 23 at both ends, and is formed inside all the film formation stations ST1 to STn. A target mechanism 61, a radical source 80 as an energy source of the active seed source, and a pipe 75 for introducing a reactive gas from the gas bottle 76 as a gas source are provided.

As shown in FIG. 2, the target mechanism 61 includes magnetron sputtering electrodes 62a and b which are opposed to the substrate 43, and targets 63a and b which are held by the magnetron sputtering electrodes 62a and b, and which are not shown. An AC power source 64 to which a transformer is connected to the magnetron sputtering electrodes 62a, b to apply an alternating electric field, and a gas bottle 65 for storing a sputtering gas composed of an inert gas such as argon gas, which is a working gas for sputtering, is introduced and stored. The mass flow controller 66 of the sputtering gas of the gas bottle 65.

The magnetron sputtering electrodes 62a, b are provided in parallel with the substrate 43 held by the substrate holder (not shown).

The targets 63a, b are disposed such that the sputtered sputtering surface is parallel to the substrate 43. Sputtering here refers to a phenomenon in which a target constituent element is bombarded by a sputtering phenomenon to cause a target to be consumed.

The targets 63a, b are commonly used in sputtering (Si), niobium (Nb), aluminum (Al), titanium (Ti), zirconium (Zr), tin (Sn), chromium (Cr), niobium ( Known metal targets such as Ta), tellurium (Te), iron (Fe), magnesium (Mg), hafnium (Hf), nickel chromium (Ni-Cr), indium tin (In-Sn), or conductive metal compounds Target or composite target composition.

The target material 63a of the present embodiment has a size of 5 × 27 inches, and the distance D between the target 63a and the substrate 43 is 70 to 400 mm.

The metal compound is formed into a film by the sputtering of the targets 63a, b in the film formation effective region A shown in Fig. 2.

The AC power supply 64 of the present embodiment is constituted by an LF power supply. However, the present invention is not limited thereto, and may be constituted by an RF power supply, a dual-frequency RF power supply, or the like.

In the present embodiment, the mass flow controller 66 guides an inert gas such as argon gas from the gas bottle 65 to the film formation station ST whose vacuum degree has been adjusted by the vacuum pump 95, and the atmosphere atmosphere of the vacuum gas in the film formation station ST is adjusted. Perform dual magnetron sputtering.

In dual magnetron sputtering, the magnetron sputter electrodes 62a, b and the targets 63a, b are used from one of the ground potential electrical insulation. Therefore, although not shown, the magnetron sputtering electrodes 62a, b and the targets 63a, b are attached to the body of the sputtering apparatus 1 that is grounded through the insulating material. Further, the magnetron sputtering electrode 62a, the target 63a, the sputtering electrode 62b, and the target 63b are also electrically separated from each other.

In this state, a working gas such as argon is introduced into the vicinity of the targets 63a and b to adjust the sputtering atmosphere, and a voltage is applied from the AC power source 64 to the magnetron sputtering electrodes 62a and b via a transformer (not shown). An alternating electric field is applied to the targets 63a, b. That is, at a certain point, the target 63a becomes a cathode (negative electrode), and at this time, the target 63b is necessarily an anode (positive electrode). When the direction of the exchange at the next time point changes, the target 63b becomes the cathode and the target 63a becomes the anode. The plasma is formed by the interaction of the cathode and the anode by a pair of two targets 63a, b as described above, and the target on the cathode is sputtered to form a metal ultra-thin film on the substrate.

At this time, although an incomplete metal having low conductivity or low conductivity is attached to the anode, when the anode is converted into a cathode by an alternating electric field, the incomplete metal is sputtered. The surface of the target becomes the original clean state. Then, by repeating this operation, the stable anode potential state can be obtained at any time, and the change in the plasma potential which is substantially equal to the anode potential can be prevented, and the metal particles can be stably scattered from the targets 63a and b to the substrate 43.

The targets 63a and 63b may also contain only the same metal, and may also contain a different metal. When a target composed only of the same metal is used, a film containing a single metal is formed, and when a target containing a different metal is used, a film composed of a compound of the alloy is formed.

The frequency of the alternating voltage applied to the targets 63a, b is preferably 10 to 120 kHz.

The radical source 80 is composed of an inductively coupled plasma generating unit having a high frequency antenna. As shown in FIG. 1 and FIG. 2, one of the downstream side of the target mechanism 61 is provided, and as shown in FIG. The dielectric plate 83, the fixing frame 84, the antennas 85a, b, the fixture 88, the piping 95a, and the vacuum pump 95 are formed.

As shown in FIG. 3, the casing 81 is made of stainless steel and has a substantially rectangular parallelepiped as an open container. Body composition. The dielectric plate 83 is fixed to block the opening, and a dielectric window is formed. The side of the inner side of the casing 81 is the antenna housing chamber 80A.

The antenna storage chamber 80A is partitioned from the film formation station ST by the dielectric plate 83 to form a space independent of the film formation station ST. The dielectric plate 83 is made of a plate-shaped known dielectric material, and is formed of quartz in this embodiment.

The fixing frame 84 is composed of a rectangular frame. The dielectric plate 83 is sandwiched and fixed between the fixing frame 84 and the casing 81 by connecting the fixing frame 84 and the casing 81 with a bolt (not shown).

Antennas 85a, b are provided in the antenna housing chamber 80A.

The antennas 85a and b are formed of a spiral coil electrode covered with silver on the surface of the tubular body made of copper. In the antenna housing chamber 80A, the spiral surface is arranged parallel to the bottom surface of the casing 81 and the dielectric plate 83.

The antennas 85a, b are connected in parallel to the high frequency power supply 89. Further, as shown in FIG. 4, the antennas 85a, b are connected to the matching box 87 including the variable capacitors 87a, b through the lead portions 86a, b, and are further connected to the high-frequency power source 89.

The fixture 88 is constituted by fixing plates 88a, b formed of a plate body in which grooves of the antennas 85a, b can be fitted, and fixing bolts 88c, d.

The antennas 85a, b are fitted to the fixing plates 88a, b, and are fixed to the casing 81 by fixing bolts 88c, d. A plurality of screw holes are formed in the casing 81 in the vertical direction, and the fixing plates 88a and b are attached to the casing 81 by using any of the screw holes.

In order to insulate the antennas 85a, b from the fixed plates 88a, b, at least the contact faces of the antennas 85a, b with the fixed plates 88a, b are formed of an insulating material.

As shown in Fig. 3, a piping 95a for exhausting is provided on the bottom surface of the casing 81, and a vacuum pump 95 is connected to the transmission valve. Thereby, the operable valve can be exhausted in the antenna housing chamber 80A by the vacuum pump 95 that exhausts the film forming station ST. Further, in Fig. 1, the piping 95a is displayed only for a part of the radical source 80.

In the present embodiment, as shown in FIGS. 3 and 4, although an inductively coupled plasma source using a planar spiral spiral antenna is used, other forms of inductively coupled plasma sources may be used. . For example, there is a type in which a high-frequency current flows through a coil formed by a helical antenna in which a glass tube is spirally wound, or a type in which an antenna is inserted into a plasma.

Further, other plasma sources that generate plasma by inductive coupling or surface waves through a dielectric window, such as an electron cyclotron resonance (ECP) plasma source, a spiral wave excitation (HWP) plasma source, and a microwave excitation surface may also be used. Wave (SWP) plasma source, etc.

Instead of the inductively coupled plasma source, a capacitively coupled plasma generating source may be used. The flat electrode is disposed inside the antenna housing chamber 80A, and high frequency power of 100 kHz to 50 MHz is applied to the flat electrode to make the plasma. produce.

Further, a plasma generating source which generates a plasma in which an inductively coupled plasma and a capacitively coupled plasma are mixed may be used.

In the film formation station ST, a pipe 75 is provided between the radical source 80 and the substrate 43 as shown in Fig. 2, and a gas bottle 76 of a reactive gas is connected to the mass flow controller 77. Thereby, the reactive gas can be introduced between the radical source 80 and the substrate 43.

In the present embodiment, an oxidizing gas such as oxygen (O ₂ ), ozone (O ₃ ) or nitrous oxide (N ₂ O), a nitriding gas such as nitrogen (N ₂ ), or methane can be used as the reactive gas ( A carbonizable gas such as CH ₄ ), a fluorine-containing gas such as fluorine (F ₂ ) or carbon tetrafluoride (CF ₄ ), or the like.

Further, in the present embodiment, the mass flow controller 66 for introducing the sputtering gas and the mass flow controller 77 for introducing the reactive gas are provided independently of each other, and are configured to be independently controllable while monitoring the deposition rate and the like. The power supply and gas flow rate of the sputtering source and the power source and gas flow rate of the active seed source are used to perform feedback control of the film formation rate.

As shown in FIG. 2, the radical source 80 is inclined so that the surface of the dielectric plate 83, that is, the surface of the dielectric window on which the dielectric plate 83 is disposed, faces the center direction of the substrate 43. The angle between the face of the dielectric plate 83 and the substrate 43 is in the range of 0° or more and less than 90°. In other words, the dielectric plate The substrate 83 is held in parallel with the targets 63a, b or at an angle of 0° or more and less than 90°, and is inclined to the substrate 43 of the substrate holder (not shown) so that the outside of the film formation station ST is close to the substrate 43.

When the angle between the surface of the dielectric plate 83 and the surface of the substrate 43 is 0 to 60, the film formation rate is the highest, which is preferable.

Further, each film formation station ST includes an optical film formation rate control device (not shown), and the film formation rate can be controlled by controlling the sputtering condition of each film formation station ST by the film formation rate control device. Film thickness.

The film formation rate control device (not shown) includes an optical film thickness meter (not shown) that measures the thickness of the film formed on the substrate 43 and the film thickness measurement result according to the optical film thickness meter. 77 is a control device not shown to control the flow of gas.

The optical film thickness meter uses a transmissive optical film thickness meter that emits light from a light projector and measures light transmitted through the optical film. However, a reflective optical film thickness meter may be used, which is used in an optical film. The film thickness is measured by a phenomenon in which the light reflected on the surface and the light reflected at the interface between the substrate and the optical film interfere with each other due to a phase difference.

During the sputtering process, the film thickness of the film formed on the substrate 43 is monitored by an optical film thickness meter (not shown) in each film formation station ST, and film formation is detected by the optical film thickness meter. When the speed is lowered, the amount of current from the AC power source 64 and the high-frequency power source 89 is increased, and control is performed to restore the lowered film forming speed to the original speed.

In the state in which the radical source 80 of the present embodiment is held in the antenna accommodating chamber 80A at a pressure lower than that in the film formation station ST, the reactive gas in the gas bottle 76 is introduced into the film formation station via the mass flow controller 77. ST. A voltage of 13.56 MHz is applied to the antennas 85a, b from the high-frequency power source 89 to cause a high-frequency current to flow. Thereby, plasma is prevented from being generated in the antenna storage chamber 80A, and the antennas 85a and b receive the supply of electric power from the high-frequency power source 89, and an induced electric field is generated inside the film formation station ST to generate plasma of the reactive gas.

In each film formation station ST, the target mechanism 61 is provided at the center of the substrate transfer direction of the film formation station ST. The radical source 80 is disposed on the downstream side of the target mechanism 61 in the substrate transport direction.

The number of film formation stations ST (ST1 to STn) constituting the film forming chamber 21 is determined as the number of layers of the multilayer film formed. When the number of the film formation stations ST corresponding to the number of layers of the multilayer film formed is set, each film formation station ST is formed into a film layer by layer. When a film formation station ST having a larger number of layers than the multilayer film is formed, at least one of the plurality of layers is formed by a plurality of film formation stations ST.

The loading space portion 22 and the unloading space portion 23 have the same configuration as the film forming station ST except that the target mechanism 61 and the radical source 80 are not provided inside.

In the present embodiment, although only one of the radical source 80 is disposed on the downstream side of the target mechanism 61 in each of the film formation stations ST, the sputtering apparatus 1' of FIG. 5 may be attached to each film formation station. In the ST, the pair of radical sources 80 are disposed on the upstream side and the downstream side of the target mechanism 61 so as to sandwich the target mechanism 61. Since the other structure of the sputtering apparatus 1' is the same as that of the sputtering apparatus 1, description is abbreviate|omitted.

Further, the radical source may be disposed only on the upstream side of the target mechanism 61.

(film formation method)

Hereinafter, a film forming method using the sputtering apparatus 1 of the present embodiment will be described.

First, the inside of the film forming chamber 21 is evacuated. Next, a predetermined number of substrate holders (not shown) are prepared to hold the large-sized substrate 43. The gate valve 12 is opened, and a predetermined number of substrates 43 are introduced into the load lock chamber 11 of the sputtering apparatus 1, and the gate valve 12 is closed. The load lock chamber 11 is evacuated from the atmospheric state until it reaches the same degree of vacuum as the film formation chamber 21.

Then, the target mechanism 61 and the radical source 80 of each film formation station ST are actuated to start sputtering, and the gate valve 13 is opened, and the first substrate 43 is introduced into the mounting space portion 22 of the film forming chamber 21.

By the substrate transfer mechanism (not shown), the substrate 43 is moved in the direction of the film formation station STn at a constant speed, and film formation is performed in the film formation stations ST1 to STn in this order.

Film formation of a metal compound is performed in each of the film formation stations ST1 to STn as follows.

After the substrate 43 conveyed by the substrate transfer mechanism is introduced into the first film formation station ST1, the substrate 43 is sequentially introduced into the film formation effective region A shown in FIG. 2 from the upstream side in the substrate transfer direction.

After the substrate 43 enters the film formation effective region A, first, in the sputtering step, the metal particles are struck from the targets 63a, b by sputtering, and the regions surrounded by the film formation effective region A and the targets 63a, b are The targets 63a, b scatter toward the substrate 43.

Next, one of the metal particles in the scattering portion becomes a metal incomplete reactant by the radical of the reactive gas formed by the radical source 80 during the period from the target 63a, b to the substrate 43. The metal particles and the metal incomplete reactant correspond to particles of the incomplete compound of the patent application.

Next, metal particles and metal incomplete reactants are deposited on the substrate 43 to form a film formation of the incomplete compound.

Next, in the composition conversion step, the film formation of the incomplete compound on the substrate 43 is converted into a complete compound of the metal by the radical of the reactive gas formed by the radical source 80.

While the substrate 43 passes through the film formation effective region A, the sputtering step and the composition conversion step are performed in parallel, and when the substrate 43 is discharged from the film formation effective region A, a metal compound film is formed on the substrate 43.

At the film formation stations ST2 to n after the second time, the same steps as those of the film formation station ST1 are performed, and a film made of a complete compound of metal is formed.

When the combination of the metals of the targets 63a and b is the same in the adjacent film formation stations STi to STi+m (i and m are positive integers), the same is formed in the adjacent film formation stations STi to STi+m. Film of the layer. That is, a film is formed in the adjacent film formation stations STi to STi+m.

On the other hand, when the combination of the metals of the targets 63a, b is different in the adjacent film forming stations STi to STi+m (i and m are positive integers), the adjacent film forming stations STi~STi+ A film of a plurality of layers is formed in m.

During the sputtering of the targets 63a, b and the radical formation of the reactive gas by the radical source 80, the film formation rate is controlled by an optical film formation rate control mechanism (not shown), and a film formation rate control mechanism According to the amount of metal, gas, and metal compound detected by an optical fiber (not shown) The mass flow controllers 66, 77 are controlled to control the gas flow rate, thereby controlling the film formation rate to a desired value. Thereby, the film thickness in each film formation station ST is controlled.

After the film formation station STn is formed and the reaction is completed, the substrate 43 is introduced into the unloading space portion 23. The unloading chamber 31 is evacuated in advance to have substantially the same degree of vacuum as the film forming chamber 21. After the gate valve 33 is opened and the substrate 43 is introduced into the unloading chamber 31, the gate valve 33 is closed, and the substrate 43 is held in the unloading chamber 31.

Next, the next substrate 43 held in the load lock chamber 11 is introduced into the film forming chamber 21, and the same film formation and thick reaction are carried out, and the same is introduced into the unloading chamber 31 and held therein. After the same processing is completed for all the substrates 43 held in the load lock chamber 11, the unloading chamber 31 is brought to an atmospheric state, the gate valve 32 is opened, and all the substrates 43 are taken out to the atmosphere to complete film formation.

By the above method, a multilayer film of a metal compound having a number of layers corresponding to the number of metals and reaction gases of the film formation station ST is formed.

When different metals and reaction gases are used between all adjacent film formation stations ST, the multilayer film becomes the number of layers corresponding to the number of film formation stations ST. When the same metal and the reaction gas are used between the adjacent film formation stations ST, a layer is formed together at the adjacent film formation station ST.

[Examples]

Specific embodiments of the invention are described below.

(Experimental Example 1)

In the present experimental example, the radical source 80 is disposed such that the surface of the dielectric plate 83 is parallel to the substrate 43 and parallel to the targets 63a, b, for the substrate 43 in the film formation station ST and the target 63a, b Films of Examples 1 to 4 in which the distance D was changed to 40 mm, 70 mm, 200 mm, and 400 mm, respectively, were formed, and the film formation rate and the obtained film were compared.

In the present embodiment, a single-layer film of cerium oxide is formed on a large-sized glass substrate having a size of 600 cm × 400 cm by the thin film forming method of the above-described embodiment using a sputtering apparatus 1 having one film forming station ST.

In the film formation station ST1, the target materials 63a, b use a ruthenium target, and argon gas 800 sccm as a sputtering gas is supplied from the gas bottle 65. An oxygen (O ₂ ) gas as a reactive gas was introduced at 80 sccm, and a radical was generated by the radical source 80.

Other specific conditions and results are shown in Table 1.

As is clear from the results of Table 1, in the case where the distance D is 40 mm, the absorption coefficient of the formed film is about 10 ^{- 3} higher. The reason for this is considered to be that if the distance D is too short, the film formation rate becomes too high, and the reaction does not follow and causes absorption.

In the case of an optical film, in order to obtain the necessary transmittance, since it is necessary to have an absorption coefficient of about 10 ^-4 , it is understood that the distance D must be longer than 40 mm.

(Experimental Example 2)

In the present experimental example, the distance D between the substrate 43 and the targets 63a, b in the film formation station ST was set to 200 mm, and the radical source 80 was inclined to the surface of the dielectric plate 83 toward the target 63a, b side. Incident, the film formation was carried out for Examples 3, 5, and 6 in which the opposite substrate 43 was changed to 0, 30, and 60, and the film formation rate and the obtained film were compared.

Other specific conditions and results are shown in Table 2. Further, other conditions of the experimental example were the same as those of Experimental Example 1.

As is clear from the results of Table 2, in the case where the surface of the dielectric plate 83 is inclined by 30° and 60° with respect to the substrate 43, the film formation rate becomes higher than that without tilting. Therefore, it is understood that by tilting the radical source 80 toward the targets 63a and b, the reactivity can be improved while maintaining a moderate absorption coefficient, so that the target power can be increased and the film formation rate can be further improved.

(Experimental Example 3)

In the present experimental example, in the sputtering apparatus 1 including one film formation station ST, a pair of radical sources 80 are provided on the upstream side and the downstream side of the clip target 63a, b in the case where the single radical source 80 is provided. In the case of film formation, the film formation rate and the obtained film were compared.

Other specific conditions and results are shown in Table 3. Further, other conditions of the experimental example were the same as those of Experimental Example 1.

As is clear from the results of Table 3, in the case where the pair of radical sources 80 are provided, the absorption coefficient is kept substantially the same as that of the case where the single radical source 80 is provided, and the film formation rate is increased by about one percent. Therefore, it is understood that by providing the pair of radical sources 80, the reactivity can be improved while maintaining a moderate absorption coefficient, so that the target power can be increased and the film formation rate can be further improved.

(Experimental Example 4)

In the present experimental example, in the case where the multilayer AR film was formed by using the sputtering apparatus 1 of the above-described embodiment, Example 8 in which each layer was formed in a single film formation station ST and an embodiment in which a plurality of film formation stations ST were formed were formed. 9, and the film formation conditions and the prepared film were compared.

The film design of the multilayer AR film of Examples 8 and 9 is such that the first layer is Si ₃ N ₄ having a physical film thickness of 123.9 nm, the second layer is SiO ₂ having a physical film thickness of 164.3 nm, and the third layer is made of physics. Si ₃ N ₄ having a film thickness of 99.5 nm and SiO ₂ having a physical thickness of 73.2 nm were used for the fourth layer.

In the eighth embodiment, a sputtering apparatus 1 having four film formation stations ST is used. In each of the film formation stations ST1 to 4, the target materials 63a, b are supplied with a target material, and the gas bottle 65 is supplied as a sputtering gas. Argon gas was 800 sccm. Further, as a reactive gas, nitrogen (N ₂ ) gas was introduced into the film formation stations ST1 and ST3 at 140 sccm, and oxygen (O ₂ ) gas was introduced into the film formation stations ST2 and ST4 at 60 sccm, and radicals were formed by the radical source 80. Si ₃ N ₄ , SiO ₂ , Si ₃ N ₄ , and SiO ₂ are formed in each of the film formation stations ST1 to S4.

Further, the substrate transport speed was 4.4 mm/s, the distance D was 200 mm, and the angle between the dielectric plate 83 and the substrate 43 was 30°.

Further specific conditions and results of Example 8 are shown in Table 4.

In the ninth embodiment, a sputtering apparatus 1 having seven film forming stations ST is used, and in each of the film forming stations ST1 to 7, a film of the same composition is formed at each adjacent one of the film forming stations ST to form a film. A total of three layers of Si ₃ N ₄ , SiO ₂ , and Si ₃ N _{4 are used} . In the film formation station ST7, the uppermost layer of SiO ₂ film is formed by a single film formation station ST. The film thicknesses of the four layers formed were the same as those of the four layers of Example 8.

Further, the substrate transport speed was 8.7 mm/s, the distance D was 200 mm, and the angle between the dielectric plate 83 and the substrate 43 was 30°.

Further specific conditions and results of Example 9 are shown in Table 5.

According to Experimental Example 4, even in Example 9 in which a plurality of film formation stations ST were provided in each layer, a film having a film thickness substantially the same as that of Example 8 having a single film formation station ST in each layer was formed. Further, in the ninth embodiment, the substrate transport speed is substantially doubled as in the case of the eighth embodiment. However, since the film formation is performed at the two film formation stations ST until the third layer, the film formation of one substrate 43 is required. The time is the same in the embodiment 9 and the eighth embodiment.

However, in the ninth embodiment, since the substrate transport speed is faster than that of the eighth embodiment, the number of the film formation stations ST included in the sputtering apparatus 1 is large, and therefore, when the substrate 43 is continuously moved in the sputtering apparatus 1 in an in-line manner The number of the substrates 43 which can be simultaneously present in the sputtering apparatus 1 is increased, and the productivity is improved.

6 is a graph showing the reflectance of the multilayer AR film formed in Example 9 at each wavelength, and the Si ₃ N ₄ having a first layer of a physical film thickness of 123.9 nm and the second layer being a physical film thickness of 164.3 nm. _{2. A} graph in which the third layer is a Si ₅ N ₄ film having a physical film thickness of 99.5 nm, and a film of a multilayer AR film having a fourth layer of SiO ₂ having a physical film thickness of 73.2 nm is designed to reflect the reflectance at each wavelength.

As shown in Fig. 6, it is understood that the multilayer AR film formed in Example 9 can achieve optical characteristics close to the film design.

(Experimental Example 5)

In the experimental example, the conditions other than the oxygen flow rate were the same as those of the experimental example 3, and the case where the oxygen flow rate was increased from 0 sccm to 200 sccm and the case where the oxygen flow rate was decreased from 200 sccm to 0 sccm was measured at 0, 60, 70, 80, 90, 110, 120, 130, 150, 200 sccm target voltage, confirmation In the case where the oxygen flow rate is increased and decreased, whether or not a so-called hysteresis is generated which is different from the change path of the target voltage of the oxygen partial pressure.

The data of the oxygen flow rate, oxygen partial pressure, increase and decrease target voltage are shown in Table 6. The graph showing the relationship between the oxygen partial pressure and the target voltage at the time of increase and decrease is shown in Fig. 7.

As can be seen from Fig. 7, in the case where the oxygen flow rate is increased and the oxygen flow rate is decreased, the change path of the target voltage with respect to the oxygen partial pressure is substantially the same, and no hysteresis which occurs in the reactive sputtering is generated.

Therefore, when the sputtering apparatus 1 of the present embodiment is used for sputtering by the thin film formation method of the above-described embodiment, it is understood that the control of the deposition rate by adjusting the oxygen flow rate is different from that of the reactive sputtering.

A‧‧‧ filming effective area

D‧‧‧Distance

ST‧‧‧ filming station

43‧‧‧Substrate

61‧‧‧ Target Agency

62a, 62b‧‧‧Magnetron Sputtering Electrodes

63a, 63b‧‧‧ targets

64‧‧‧AC power supply

65,76‧‧‧ gas bottles

66,77‧‧‧Flow Controller

75, 95a‧‧‧Pipe

80‧‧‧Free radical source

83‧‧‧Dielectric board

87‧‧‧match box

89‧‧‧High frequency power supply

95‧‧‧vacuum pump

Claims (15)

A thin film forming apparatus which is formed by sputtering a thin film of a metal compound on a substrate in a vacuum chamber, wherein the vacuum chamber is provided with a target material composed of a metal or a conductive metal compound; The active seed source is formed to interact with the target electromagnetically and under pressure to generate an active species of a reactive gas; the target material is disposed opposite to the substrate; and the active seed source is provided with the reactive gas a gas source and an energy source for supplying energy into the vacuum chamber to excite the reactive gas into a plasma state; the energy source being provided between the vacuum chamber and the vacuum chamber for supplying the energy to the vacuum chamber a dielectric window; the dielectric window is disposed to be inclined toward the target side at an angle of less than 90° with respect to the substrate located at a position opposite to the energy source. The thin film forming apparatus according to claim 1, wherein the dielectric window is disposed to be inclined toward the target side at an angle of 30 or more with respect to the substrate, and the substrate is perpendicular to a transport direction of the substrate. The direction is located opposite the aforementioned energy source. The film forming apparatus according to the first aspect of the invention, comprising: a substrate transport unit that transports the substrate in the vacuum chamber; and at least one of an upstream side and a downstream side of a transport direction of the substrate in the target material; Source. The film forming apparatus according to the first aspect of the invention, comprising: a substrate transfer unit that transports the substrate in the vacuum chamber; and the active seed source on an upstream side and a downstream side of a transport direction of the substrate in the target material. The film forming apparatus of claim 1, wherein the sputtering gas controller for controlling the flow rate of the sputtering gas introduced into the target and the reactive gas controller for controlling the flow rate of the reactive gas are independently set And a detection unit for optically detecting a film formation rate; and a control device for receiving a signal from the detection unit, at least independently controlling the sputtering power source and the sputtering gas controller, and the activity The source power source and the aforementioned reactive gas controller are used to control the film formation rate. The film forming apparatus according to claim 1 or 2, wherein the energy source generates a plasma source of plasma by inductive coupling or surface wave through the dielectric window. The film forming apparatus according to claim 1 or 3, wherein the active seed source is an inductively coupled plasma (ICP) radical source. The film forming apparatus according to claim 3, wherein the film forming apparatus comprises an in-line sputtering apparatus including a plurality of film forming stations, wherein the film forming station includes the target and the aforementioned The active seed source of at least one of the upstream side and the downstream side of the substrate transport direction. The film forming apparatus according to claim 8, wherein the film forming station includes a detecting unit that optically detects a film forming rate, and includes a signal for receiving a detecting unit from the film forming rate to control each of the forming units. Control device for individual film formation rates of membrane stations. The film forming apparatus according to claim 1 or 3, further comprising: a sputtering unit that sputters the target in the vacuum chamber, and the particles of the incomplete compound are scattered from the target to the substrate by the sputtering And a composition conversion unit, wherein the active species of the reactive gas generated by the active species source are contacted with the particles in the vacuum chamber to be converted into a complete compound of the metal; and the substrate can be formed on the substrate A film composed of a complete compound of metal. A sputtering cathode is a film in which a metal compound is formed by sputtering on a substrate in a vacuum chamber provided in a thin film forming apparatus, and comprises: a target material made of a metal or a conductive metal compound; The active seed source is formed to interact with the target electromagnetically and under pressure to generate an active species of the reactive gas; the active seed source has a gas source for supplying the reactive gas, and supplies energy to the vacuum An energy source for exciting the reactive gas into a plasma state in the tank; the target material is disposed opposite to the substrate; and the energy source is provided with a dielectric window for supplying the energy to the outside of the energy source; The dielectric window is disposed to be inclined toward the target side at an angle of less than 90° with respect to the substrate located at a position opposite to the energy source. The sputter cathode of claim 11, wherein the target material and the active species are sourced in the same space of the vacuum chamber, and the sputtered surface of the target which is sputtered is opposed to the active seed source. The substrate and the active species source are located at least one of an upstream side and a downstream side in a transport direction of the substrate of the target. A method for forming a thin film, comprising: a sputtering step of sputtering a target made of a metal or a conductive metal compound disposed opposite to a substrate in a vacuum chamber, wherein the sputtering is performed from the target a particle of the complete compound is scattered toward the substrate; and a composition conversion step is provided, wherein the substrate in the vacuum chamber is inclined toward the target side at an angle of less than 90° with respect to the substrate located opposite to the energy source Supplying energy to the dielectric window in the vacuum chamber to generate a reactive gas generated by an active species source of an active species that forms a reactive gas that is electromagnetically and pressure-sensitive to each other The active species is contacted with the particles to be converted into a complete compound of the metal; by having the above two steps, a complete compound of the foregoing metal is formed on the substrate Into the film. The film forming method of claim 13, wherein the reverse film forming step is performed by repeating the sputtering step and the composition converting step in parallel after the composition converting step. The method for forming a film according to claim 13 or 14, wherein the step of introducing the substrate into an in-line type thin film forming apparatus including a plurality of film forming stations, wherein the film forming station includes the target material, is performed before the sputtering step And an active seed source provided on at least one of an upstream side and a downstream side of a transport direction of the substrate of the target; and an in-station film forming step of forming the substrate in the film forming station Carrying out the sputtering step, the composition conversion step, and the reverse film formation step at a constant speed, and performing a transfer step of transporting the substrate to the film formation station on the downstream side in the transport direction of the substrate; and repeating the above-mentioned station The film forming step and the plurality of station forming steps of the transporting step; and the step of discharging the substrate into the atmosphere after performing the in-situ film forming step at the film forming station located at the most downstream of the substrate transport direction.